Linear correlations of Gibbs free energy for rare earth element oxide, hydroxide, chloride, fluoride, carbonate, and ferrite minerals and crystalline solids

TL;DR

This paper develops a linear free energy relationship model to accurately predict Gibbs free energies of formation for various REE minerals, improving thermodynamic data consistency for geochemical applications.

Contribution

It introduces a new method using Sverjensky LFER to estimate Gibbs free energies of REE minerals, enhancing data accuracy and consistency across mineral families.

Findings

Provides a set of consistent Gibbs free energies for 119 REE minerals.

Improves thermodynamic modeling of REE mineral stability at high pressures and temperatures.

Creates a new database for high P-T thermodynamic calculations.

Abstract

Rare Earth Elements (REE) are critical minerals (metals) for the transition from fossil fuels to renewable and clean energy. Accurate thermodynamic properties of REE minerals and other crystalline solids are crucial for geochemical modeling of the solubility, speciation, and transport of REE in ore formation, extraction, chemical processing, and recycling processes. However, the Gibbs free energies of formation (DGof, REEX) for these solids from different sources vary by 10s kJ/mol. We applied the Sverjensky linear free energy relationship (LFER) to evaluate their internal consistency and predict the unavailable DGof of the REE solids. By considering both the effects of ionic radius size and corresponding aqueous ion properties, the Sverjensky LFER allows estimates with much accuracy and precision. Here, rREEZ+ represents the Shannon-Prewitt ionic radii of REEZ+, and DGon, REEZ+ denotes the non-solvation contribution to the DGof of the aqueous REEZ+ ion. X represents the remainder of the compounds. In this study, the parameters aREEX, bREEX, and beta REEX were regressed from DGof compilations in the literature for 13 isostructural families. Based on these linear relationships, we recommend a set of internally consistent DGof, REEX for 119 end-members of REE oxides, hydroxides, chlorides, fluorides, carbonates, hydrous carbonates, and ferrites. These DGof, REEX are combined with experimental or predicted values of So, Vo, and Cpo from the literature and incorporated into a new SUPCRT database, which allows the calculations of thermodynamic properties to high P-T conditions (e.g., up to 1000 oC and 5 kb).